Lubricant for processing metals



Patented May 13, 1947 UNITED STATES PATEN LUBRICANT FOR PROCESSINGMETALS Joseph Barrel Shlpp, Wilmington, Del., and

Charles J. Pedersen, Penns Grove, N. J assignors to E. I. du Pont deNemours & Company, Wilmington, Del., a corporation of Delaware NoDrawing. Application May 26, 1945, Serial No. 596,078

20 Claims.

This invention relates to new compositions of matter and particularly toaqueous emulsions especially adapted forlubricating metals duringprocessing operations, such as cutting, drawing,

drilling, tapping, milling, stamping and the like.

machines, it is very difficult to keep a lubricant at the cutting pointdue to the continual flow of metal past this point under extremepressures. The ideal lubricant would be one which could be applied tothe cutting edge before cutting was begun, and which would clingtenaciously to that edge and facilitate the sliding of the metalsurfaces by the cutting edge. Without proper lubrication at the cuttingedge, there is a tendency for metal to build up on the cutting tool andthis impairs cutting. Likewise, in other metal cutting operations wherehigh pressures are involved, there is a tendency for metal to metalcontact between cutting tool ordie and metal being processed, unless atenacious lubricant is used. As a result, there is a welding of the twometals which eventually causes scoring or tearing out of metal, giving arough surface to the object being processed. This problem exists incutting, drawing, stamping and other operations.

In the cutting of soft metals, the difliculty is accentuated due to thelow resistance of the metals to deformation under pressure. Thus, intapping holes in aluminum, there is a tendency to tear out the metal andgive an over size hole unless a highly efiicient lubricant is used. Dueto this fact, it was difficult to get close fitting threads in alum num.It has been customary to use under-size taps in tapping aluminum andother soft metals. This necessitates two sets of taps where one set oftaps would be sufiicient if a satisfactory lubricant were used. Intapping hard metals to give close clearance threads, there is also sometendency for some of the harder crystals of some alloy metals to bepulled out rather than out through. This results in an unevenly cutsurface. To minimize the tearing out of these crystals, it is oftennecessary to resort to laborious hand tapping to obtain closeclearances.

It is an object of the present invention to provide new and usefulemulsions. Another object is to provide novel emulsions particularlyadapted for lubricating metals during metal processing perations. Stillanother object is to provide improved metal processing lubricants, andparticularly lubricants which are stable and non-corros ve towardmetals. Other objects are to provide new compositions of matter and toadvance the art. Still other objects will appear hereinafter,

The above and other objects may be accomplished in accordance with ourinvention which comprises providing an aqueous emulsion of a Lorolresidue in which the emulsifying agent is a surface-active water-solublenon-acidic salt of an acid-ester of phosphoric acid. We have found thatsuch emulsions are effective lubricants for metal processing operations,such as cutting, drawing, drilling, tapping, milling, stamping and thelike. Such emulsion is particularly effective as a lubricant in tappingboth hard and soft metals and in cutting, drilling and drawing of softmetals.

The term Lorol residue, as employed herein and in the claims, means thedistillation residue of a hydrogenated fatty oil. The Lorol residue isobtained by the carboxyl hydrogenation of a natural fatty oil in thepresence of a hydrogenation catalyst until the major proportion, atleast of the carboxyl groups have been reduced, followed by separationof the hydrogenation catalyst and distillation of the reaction mixtureto remove substantially all alcohols up through octadecyl alcohol.

Suitable methods of carrying out the hydrogenation are well known andare illustrated by those disclosed in Patent 2,023,383 to Schrauth eta1. and Patent 2,094,127 to Lazier. Since the original esters,constituting the major proportion of the fatty oils, do not have thedesired lubrieating properties, the hydrogenation should be carried outso as to obtain substantially complete reduction of the carboxyl groups,that is, as far as is practicable.

After the hydrogenation, the mixture is filtered to remove the catalyst.The reaction mixture is then subjected to a distillation to distill offsubstantially all alcohols up through octadecyl alcohol. Thisdistillation will preferably be carried out under reduced pressure. Theresidue left in the still is a Lorol residue. It is a product ofindeterminate composition and appears to contain higher alcohols, estersof higher alcohols, ethers of higher alcohols, hydrocarbons, glycerlneand esters of glycerine with the ethers of the higher alcoholspredominating. A typical Lorol residue gave the following data onanalysis:

Frequently, it is desirable to subject this residue to a furtherhydrogenation and distillation S as. to recover more of the valuablealcohols and to reduce the proportion of esters in the residue.

The Lorol" residue may be derived from any- Many of the commonemulsifying agents will be effective to emulsify the Lorol residue inwater. However, most of such emulsifying agents are unsuitable for thereason that the resulting emulsions will cause corrosion or rusting ordiscoloration of the metals, and particularly such metals .as iron,aluminum and copper.

We have found that the water-soluble nonacidic salts of the acid-estersof phosphoric acid which are surface-active, that is, which haveemulsifying properties, are particularly effective for emulsifying Lorolresidues in water to produce non-corrosive, non-rusting andnon-discoloring emulsions. An acid-ester of phosphoric acid is one inwhich from 1 to 2 of the hydrogens of phosphoric acid has been replacedby an esterifying group and which contains from 1 to 2 unreplacedhydrogen atoms. The esterifying group may be any organic group whichimparts substantial surface activity to the compound. Suitableesterifying groups are long-chain alkyl, alkyl substituted aryl, aralkyland the like. Aryl groups may also be present, particularly when mixedwith long-chain alkyl groups. By longchain alkyl," we mean open-chainaliphatic hydrocarbon groups of 8 or more carbon atoms. Preferably, thelong-chain alkyl groups will contain from 8 to 20 carbon atoms.Representative long-chain alkyl groups are octyl, decyl, dodecyl,tetradecyl, hexadecyl and cetyl. Suitable alkyl substituted aryl groupsare isopropylnaphthyl, laurylphenyl and the like. Preferably, theacidesters will be mixtures of mono and di-esters containing about 1.5esterifying groups for each phosphate radical. The esterifying groupsmay be a mixture of 2 or more different groups, at least one of whichmust impart appreciable surface activity to the compound. Best resultshave been obtained with acid-esters containing about 1.5 long-chainalkyl groups of 8 to 18 carbon atoms per phosphate radical.

The salts of the acid-esters are those in which the ester has beencompletely neutralized by a basic salt-forming substance which forms,with the ester, a surface-active water-soluble salt.

Suitable basic salt-forming substances include primary, secondary andtertiary amines, particularly mono-, diand trialkylamines andalkylolamines. Preferably, the basic salt-forming substance will be ashort-chain aliphatic amine and particularly an alkylolamine, such astriethanolamine. The basic salt-forming substance may be ammonia or analkali metal, but these are not preferred since the resulting salts areless eilective and are less desirable because of a tendency to producecorrosive products. The basic saltforming substance maybe used in excessprovided that it does not produce a pH in excess of 10 in the finalproduct as a 10% solution. With the less basic amines and thealkylolamines, an excess of up to of that required to neutralize theester may be used. With strong bases care must be taken to avoid suchexcess as will cause corrosion of the metals. I

The concentration of the Lorol" residue in the emulsion may be widelyvaried in accordance with the use to which it is to be put. Where theemulsion is to be employed as a coolant, as well as a lubricant, andapplied by a circulating pump or the like, the Lorol" residue should bepresent in a concentration of from about 1% to about 5% and preferablyfrom about 2% to about 4%. Where the lubricant is to be applied to thework and tool by brushing or the like, the Lorol residue will be presentin the emulsion in a concentration of approximately 10%. Ordinarily, theemulsion will be marketed as a concentrate to be further diluted foruse. In such concentrate, the "Lorol" residue will usually be present ina concentration of from about 40% to about 55%. The concentratedemulsion may contain higher concentrations of Lorol residue up to about70%, but such concentrations'will usually be undesirable as they arequite viscous and are difficult to stir into water to obtain the desireddiluted emulsion for use.

The proportion of the emulsifying agent in the emulsion may be widelyvaried and will be largely dependent upon the effectiveness thereof asan emulsifying agent. For practical purposes, suflicient emulsifyingagent should be used to provide a stable emulsion. A substantialincrease of the emulsifying agent over that required to provide a stableemulsion will usually be undesirable because it increases the tendencyof the emulsion to foam during use. We have employed satisfactorilyproportions of emulsifying agent ranging from as little as 2% to as muchas 50% based on the Lorol residue. With the preferred emulsifyingagents, we have obtained very satisfactory results employing from about3% to about 10% of the emulsifying agent based on the Lorol residue.

Representative concentrated preparations, which have been employedsatisfactorily in commercial applications, had the followingcompositions:

. Parts Parts Lorol" Residue 40 40 Pine Oil 12 12 Alkyl phosphate l. 5Triethanolamine l. 5 Water 45. 00

1 This is a mixture of esters of phosphoric acid containing about 1.5alkyl groups per phosphoric acid radical, the alkyl groups being derivedfrom a mixture of primary straight-chain aliphatic alcohols of 8 to 14carbon atoms.

In order to more clearly illustrate our invention, the preferred modesof carrying the same into effect and advantageous results to be obtainedthereby, the following examples are given:

Example 1 assume hydrogenating' to further convert esters into alcohols,and distilling oil these alcohols, was heated to 60 C., at whichtemperature it was molten. This molten residue was then poured slowlyinto the triethanolamine-lauryl-phosphate solution with vigorousstirring. The residue was emulsifled to give a particle size of 2 to 3microns. A thick creamy emulsion was formed which could be readilydispersed in hot water.

Example 2 One and one-half grams of the mixed mono and di-octyl estersof phosphoric acid, containing about 1.5 octyl groups per phosphateradical, and one and one-half grams dicyclohexylamine were dissolved in45 lbs. water and the solution heated to 60 C. To this solution wasadded, with stirring, 52 lbs. of the distillation residue left in thestill after distilling off the alcohols up through octadecyl alcoholfrom a hydrogenated palm oil. A thick creamy emulsion was obtained.

Example 3 The emulsion, described under Example 1, was diluted by addingparts of water to 1 part of the emulsion. This diluted emulsion was thenused as a coolant and lubricant for drilling a 1% inch hole in a 2% inchsteel rod 10 feet long. By the use of this coolant and lubricant, it waspossible to drill at a much more rapid rate than had been possible withmineral oil lubricants. Furthermore, a smoother hole was drilled and thetool life was increased. Another advantage of the aqueous system in thisdrilling operation was that the chips were removed more efiiciently, sothat drilling could be carried on continuously. In this operation, thecoolant-lubricant was pumped through holes through the drill so that itflowed back over the drill, carrying the chips with it.

Example 4 The emulsion, described in Example 2 above, was used tolubricate a tap during the tapping of a 5/ inch hole in an aluminumcasting. The emulsion was brushed onto the tap during the tappingoperation After the tap was removed, the hole was found to be properlythreaded when tested with a go-no go gauge. This gauge is so designedthat, when a hole is properly threaded, the go end of the gauge willscrew into the hole very snugly and the no go and will not screw intothe hole at all. With other lubricants, it had been found that the goend of the gauge fitted very loosely in the threaded hole and even theno go end would screw into the hole, With ordinary lubricants, it waspossible to obtain reasonably good fits only by using under-size taps.No corrosion or staining of the aluminum occurred with the emulsion.

Example 5 The emulsion, described in Example 1, was used as a. lubricantin the tapping of 1% inch holes in a chrome-manganese steel plate. Anexceedingly close fitting thread was specified. Using previouslyavailable lubricants, it was possible to obtain a, class three threadonly when resorting to hand tapping. This required eight hours of timefor the tapping of a given number of holes. When the emulsion, describedin Example 1, was used and applied by brushing onto the taps, it wasfound that a much cleaner cut and a much better class of thread wasobtained. It was possible to tap these holes by machine with thislubricant and obtain a very high quality thread- 6 withinspecifications. By the machine tapping operations, it was possible tocut downthe time required from eight hours to two hours for one unit ofthis work. No corrosion of the metal was noted in this operation.

Example 6 Forty lbs. of residue, left in the still after distilling ahydrogenated cocoanut oil, hydrogenated according to U. S. Patent2,023,383, was mixed with 10 lbs. of pine oil and then emulsified with50 lbs. of a 5% aqueous solution of the triethanolamine salt of a mixeddodecyl and decyl phosphate by stirring with a high speed stirrer. Thephosphate was prepared from a mixture of equal parts of dodecyl anddecyl alcohols and contained about 1.5 alkyl groups per phosphateradical. The pine oil was added to inhibit foaming of the emulsionduring use. The resulting emulsion was diluted with 10 parts of waterfor 1 part of emulsion, and the diluted emulsion used as a coolant andlubricant in drawing dynamite blasting caps from aluminum stampings.These dynamite caps were extremely thin walled and yet there was noindication of tearing or scoring when the above lubricant was used. Withordinary lubricants, it had been noted that a large number of caps hadtorn edges and scored surfaces. It was also noted that, with thelubricant prepared according to this invention, the life of the dies wasgreatly increased. Similar blasting caps were drawn from gilding metal,which is a high copper content alloy, and an equal improvement was notedover the use of other lubricants. There was no corrosion of the brightsurface of either the aluminum or the gilding metal, even when thelubricant was left in contact with the metal for several hours.

Example 7 A one inch rod of cold rolled steel was threaded, using theconcentrated emulsion described in Example 6 as lubricant. The lubricantwas brushed onto the metal and onto the die during hand threading. Thesurfaces of the out threads were examined under a magnification of tentimes. It was noted that an extremely smooth out was obtained, whencompared with a similar rod threaded with the same die, but using asuliurized cutting oil as lubricant. Likewise, a one inch hole wastapped in a high carbon steel, using the emulsion of Example 6 aslubricant. After tapping, the metal was cut through the hole and thethreads viewed under ten-power magnification. Again it was observed thata very smooth out had been obtained.

Example 8 A sample of olive oil was hydrogenated by the proceduredescribed in U. S. Patent 2,094,127. The hydrogenation mass was filteredtoremove the catalyst and then subjected to distillation underdiminished pressure to distill ofi the alcohols formed by hydrogenation.When substantially all of the alcohols up through octadecyl alcohol hadbeen removed, the residue was again hydrogenated and a seconddistillation carried out. The residue, from this distillation, was thenemulsified by heating it to 60 C. and adding it to a solution containing1/;;% of the triethanolamine salt of an alkyl phosphate containin about1.5 alkyl groups per phosphoric acid residue, the alkyl groups being amixture of octyl and cetyl in the ratio of 6 cetyl to 4 octyl groups.Fift grams of the hydrogenation residue were emulsified in 50 grams ofthe aqueous solution. The resulting emulsion was diluted with 4 parts ofwater and the dilute emulsion was used as a lubricant in the chasing ofthreads on a stainless steel valve stem in diameter. A very smoothsurface cut was obtained and the threads were free of the ridge cracksand checking noted with most lubricants.

Example 9 Twenty pounds of pine oil were added to 40 lbs. of the residuefrom the distillation of hydrogenated cotton seed oil. The pine oil andresidue were heated to 60 C. and poured with violent stirring into 50lbs, of water containing 4% of the salt of Z-amino 2-methyl propanol-land decyl phosphoric acid in which 1% alkyl groups are present for eachphosphoric acid unit. This emulsion was diluted with 20 parts of waterand used as a coolant and lubricant for tapping holes in aluminum alloycrank cases. The purpose of the pine oil in this example was to preventexcessive foaming of the emulsion. With this lubricant, very clean cutthreads were obtained using standard size taps and a close fit was alsoobtained as shown by the go-no go gauge. A similar emulsion, except thatthe pine oil was omitted, foamed to an objectionable degree but thefoaming was overcomeby the addition of pine oil.

Example 10 Seven and one-half pounds of a mixture of mono and di-laurylphosphates, containing about 1.5 lauryl groups per phosphate radical,was added to 27 pounds of water. Seven. and onehalf pounds oftriethanolamine was added and the solution heated to 60 C. Eighteenpounds of "Tetralin was added to forty pounds of a "Lorol residueobtained from cocoanut oil and this mixture heated to 60 C. The Lorolresidue-Tetralin" solution was then added to the aqueous solution withvigorous stirring. A creamy emulsion was obtained which could be readilydiluted with water. One pound of this emulsion was diluted with fifteenpounds of water and placed in a circulating system of a pipe threadingmachine. This machine was used for threading various size iron pipes.Microscopic examination of the cut surfaces of the threads showed a muchsmoother cut than had previously been obtained with a mineral oillubricant. The

tool life of the dies was also increased over that observed with mineraloil lubricant.

Example 11 This example is given for comparative purposes to furtherillustrate the advantages of the Lorol residue compositions of ourinvention. Tapping compounds were made up as follows:

1A mixture of esters of hosphoric acid containing about 1.5 alkyl groupsper p osphoric acid radical, the alkyl groups being derived from amixture of primary straight-chain aliphatic alcohols of 8 to 14 carbonatoms.

The emulsions were made up to approximately the same consistency as thatof Example 4 and used to lubricate a new tap in the tapping of aluminum.When the tapped holes were tested for a class 3 fit with a "go-no gogauge, the above compositions were found to be unsatisfactory becausethe holes were oversize as shown by the fact that both ends of the gaugewould screw into the holes. Also, when the holes and the taps werecarefully cleaned and the taps were screwed back into the holes, theholes, obtained with the above lubricants, gave loose fits; whereas,under the same conditions, the holes, obtained with the compositions ofour invention, gave very snug fits.

It will be understood that the foregoing examples are given forillustrative purposes solely and that our invention is not to be limitedto the specific embodiments disclosed therein, but that many variationsand modifications can be made without departing from the spirit or scopeof our invention. For example, "Lorol residues may be prepared fromother vegetable oils and animal oils. Also, other salts of otheracidesters of phosphoric acid, which are emulsifying agents, may besubstituted for those specifically mentioned.

By the use of the lubricants of our invention, there results a smoothlycut surface with very little scoring. They have been employedsatisfactorily in th processing of such metals as aluminum, varioussteels, magnesium, copper and brass. This is readily demonstrated intapping, threading, drawing, drilling, milling and turning operations.These beneficial effects are particularly apparent when theseoperation-s are carried out on soft metals, such as copper, zinc,aluminum and magnesium. Thus, in the drawing of extremely thinned walleddynamite blasting caps, there is usually a considerable tearing of thethin metal unless a lubricant of our invention is employed. Even whenthe metal is not tom, the surface may be scored to such an extent thatthe blasting cap is untrustworthy. By the use of the lubricants of ourinvention, it has been possible to greatly decrease the number ofrejected blasting caps in such operations. tapping of small holes inhard steel gun parts, it has been possible to greatly decrease thenumber of taps broken with other commonly employed lubricants.

The Lorol residues, employed in our emulsions, have usually beenconsidered as waste materials. By our invention, we have :been able tofind a valuable use for such waste materials and, at the same time, toprovide new and improved non-corrosive lubricants for the processing ofmetals. 4

We claim:

1. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic salt of a long-chain alkyl acid-ester ofphosphoric acid, the distillation residue being present in a.concentration of from about 1% to about 70% and Likewise, in the 9 theemulsifying agent being present in a minor proportion sufilcient to forma substantially a ulsion.

f im queous emulsion of a distillation residue derived from ahydrogenated vegetable oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic salt of a long-chain alkyl acid-ester ofphosphoric acid, the distillation residue being present in a.concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufiicient to form a substantiallystable emulsion.

3. An aqueous emulsion of a distillation residue derived fromhydrogenated cocoanut oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic salt of a long-chain alkyl acid-ester ofphosphoric acid, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sulficlent to form a substantiallystable emulsion.

4. An aqueous emulsion of a distillation residue derived fromhydrogenated palm oil by distilling ofi fractions up through octadecylalcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic salt of a long-chain alkyl acid-ester ofphosphoric acid, the distillation residue being present in aconcentration of from, about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

5. An aqueous emulsion of a distillation residue derived fromhydrogenated cotton seed oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic salt of a long-chain alkyl acid-ester ofphosphoric acid, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

6. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fattyoil by distilling off fractions up throughbctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic aliphatic amine salt of a long-chain alkylacid-ester of phosphoric acid, the distillation residue being present ina concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

7. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activeWater-soluble non-acidic alkylolamine salt of a long-chain alkylacid-ester of phosphoric acid, the distillation residue being present ina concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufiicient to form a substantiallystable emulsion.

8. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling 01f fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble non-acidic triethanolamine salt of a long-chain alkylacid-ester of phosphoric acid, the distillation residue being present ina concentration of from about 1% to about 70% and the emulsifying agentbeing pres- 10 ent in a minor proportion sufficient to form asubstantially stable emulsion. v

9. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling oil fractions up throughoctadecyl alcohol, in which the emulsifying agent is asurface-active'water-soluble mixture of non-acidic salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

10. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble mixture of nonacidic aliphatic amine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups "per.phosphate radical, the distillation residue being present in a'concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

11. An aqueous emulsion of a distillation resi-- due derived from ahydrogenated natural fatty oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble mixture of nonacidic alkylolamine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufiicient to form a substantiallystable emulsion.

12. An aqueous emulsion of a distillation residue derived from ahydrogenated natural fatty oil by distilling oflE fractions upthrough'octadecyl alcohol, in which the emulsifying agent is asurface-active water-soluble mixture of non-acidic triethanolamine saltsof long-chain alkyl esters of phosphoric acid containing about 1.5 alkylgroups per phosphate radical, the distillation residue being presr it ina concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion suflicient to form a substantiallystable emulsion.

13. An aqueous emulsion of a distillation residue derived from ahydrogenated vegetable oil by distilling oif fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surfaceactivewater-soluble non-acidic aliphatic amine salt of a long-chain alkylacid-ester of phosphoric acid, the distillation residue being present ina concentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

14. An aqueous emulsion of a distillation residue derived from ahydrogenated vegetable oil by distilling oif fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activeWater-soluble mixture of non-acidic aliphatic amine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

An queous emulsion of a distillation residue derived from a hydrogenatedvegetable oil by 11 distilling oif fractions up through octadecyl a1-cohol, in which the emulsifying agent is a surface-active water-solublemixture of non-acidic alkylolamine salts of long-chain alkyl esters ofphosphoric acid containing about 1.5 alkyl groups per phosphate radical,the distillation residue being present in a concentration of from about1% to about 70% and the emulsifying agent being present in a minorproportion suflicient to form a substantially stable emulsion.

16. An aqueous emulsion of a distillation resi due derived from ahydrogenated vegetable oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble mixture of non-acidic triethanolamine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifyingagentbeing present in a minor proportion sufficient to form a substantiallystable emulsion.

17. An aqueous emulsion of a distillation residue derived fromhydrogenated cocoanut oil by distilling ofi fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble mixture of non-acidic allgvlolamine salts of long-chainalkylesters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration f from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufllcient to form a substantiallystable emulsion.

18. An aqueous emulsion of a distillation residue derived fromhydrogenated cocoanut oil by distilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surface-activewater-soluble mixture of non-acidic triethanolamine salts of long-chainalkyl esters.

of phosphoric acid containing about 1.5 alkyl groups per phosphateradical, the distillation res- Certificate of Patent N 0. 2,420,328.

12 idue being present in a concentration of from about 1% to about andthe emulsifying agent being present in a minor proportion sufficient toform a substantially stable emulsion.

19. An aqueous emulsion of a distillation residue derived fromhydrogenated palm oil by dis-- tilling off fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surfaceactivewtaer-soluble mixture of non-acidic triethanolamine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion sufllcient to form a substantiallystable emulsion. V

20. An aqueous emulsion of a distillation residue derived fromhydrogenated cotton seed oil by distilling ofl fractions up throughoctadecyl alcohol, in which the emulsifying agent is a surfaceactivewater-soluble mixture of non-acidic triethanolamine salts of long-chainalkyl esters of phosphoric acid containing about 1.5 alkyl groups perphosphate radical, the distillation residue being present in aconcentration of from about 1% to about 70% and the emulsifying agentbeing present in a minor proportion suflicient to form a substantiallystable emulsion.

JOSEPH HARREL SHIPP. CHARLES J. PEDERSEN.

REFERENCES CITED The following references are of record in the file ofthis patent:

v UNITED STATES PATENTS Number May 13, 1947.

JOSEPH HARREL SHIPP ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows: Column 2,line 49, in the table, for the numeral 380 read 58; column 12, line 9,claim 19, for wtaer read water; and that the said Letters Patent shouldbe read with these corrections therein that the same may conform to therecord of the case in the Patent Ofiice.

Signed and sealed this 1st day of July, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

